Stabilization of organic substances



United States Patent 3,271,312 STABILIZATION OF ORGANIC SUBSTANCESHenryk A. Cyba, Evanston, Ill., assignor to Universal 011 ProductsCompany, Des Plaines, 111., a corporation of Delaware N0 Drawing.Original application Nov. 19, 1962, Ser. No. 238,773. Divided and thisapplication Feb. 12, 1965, Ser. No. 432,404

6 Claims. (Cl. 252-465) This is a division of copending applicationSerial No. 238,773, filed November 19, 1962, and relates to thestabilization of organic substances.

Most organic substances undergo deterioration due to oxidative reactionsand the present invention provides a novel method of preventing suchdeterioration. Deterioration of organic substances also is caused byozone, heat, mechanical action, etc., and such deterioration also is retarded by the present invention.

Deterioration of organic-substances is prevented by incorporatingtherein an inhibitor selected from the group consisting ofalpha-substituted dithiophosphatyl ketone, ketal and thioketalderivatives thereof.

The .alphasubstituted dithiophosphatyl ketone is represented by thefollowing formula:

where O is oxygen, S is sulfur, P is phosphorus, C is carbon, R and R'are selected from the group consisting of hydrogen and hydrocarbon, R isselected from the group consisting of hydrogen, hydrocarbon, halogen anddithiophosphatyl and X is selected from the group consisting of hydrogenand halogen.

The keta'l and thioketal derivatives of the alpha-substituteddithiophosphatyl ketone are represented by the following formula:

where R, R, R" and X have the same connotations as hereinbefore setforth, Y is selected from the group consisting of oxygen and sulfur, andR is selected from the group consisting of hydrogen and hydrocarbon.

Where R, R, R" and/or R in the above formulas are hydrocarbon, theypreferably are alkyl groups and more particularly alkyl groups of from 1and still more particularly from 3 to 20 carbon atoms each. Otherhydrocarbon groups included in the present invention are cycloalkyl andmore particularly cyclopentyl and cyclohexyl, alkaryl and moreparticularly alky-lphenyl and alkynaphthyl in which the alkyl groupcontains from 1 to 20 carbon atoms, aryl and more particularly phenyland naphthyl, aralkyl and more particularly phenylalkyl andnaphthylalkyl in which the alkyl contains from 1 to 20 and still moreparticularly from 1 to 6 carbon atoms, alkylcycloalkyl andcycloalkylalkyl in which the alkyl contains from 1 to 20 carbon atoms,etc. It is understood that these groups, in turn, may containnonhydrocarbon substituents attached thereto and particularlysubstituents containing halogen and more particularly chlorine, sulfur,oxygen, nitrogen, phosphorus, or mixtures thereof.

Referring to the first formula above set forth, in one preferredembodiment of the invention R and R are alkyl groups of from 1 to 20 andmore preferably from 3 to 3,271,312 Patented Sept. 6, 1966 carbon atoms,X is hydrogen and R" is hydrogen or an alkyl group of from 1 to 6 carbonatoms, or R" is a dithiophosphatyl group and more particularly the sameas the other dithiophosphatyl group.

Referring to the second formula above set forth, in one preferredembodiment of the invention R and R are alkyl groups of from 1 to 20 andpreferably from 3 to 15 carbon atoms, at least one X is chlorine, Y issulfur and R" is an alkyl group of from 1 to 6 carbon atoms or R is adiothiophosphatyl group and more particularly the same as the otherdithiophosphatyl group, and R' is an alkyl group of from 1 to 6 carbonatoms.

The novel compounds of the present invention are readily prepared by thereaction of an alkali metal dithiophosphate and an alpha-haloketone inthe presence of an oxygen-containing polar solvent. It is essential thatthe reaction is effected in the presence of the polar solvent in orderto form the novel compounds of the present invention by the interactionof the alkali metal component of the dithiophosphate with the halogencomponent of the haloketone. When using a non-polar solvent, entirelydifferent reaction products may be obtained, apparently constituting anaddition-type reaction in which both the alkali metal and the halogenare retained in the final product.

It also is essential that the haloketone used in preparing the novelcomposition of the present invention is an alpha-haloketone. In otherwords, at least one halogen should be positioned on the carbon atomadjacent to the keto group.

In a preferred embodiment the alpha-haloketone is an alpha-chloroketone.Preferred alpha-chloroketones include alpha-chloroketone(monochloroketone) and dichloroketone. In another embodiment thechloroketone comprises trichloroketone, tetrachloroketone orhexachloroketone. While the chloroketones are preferred, it isunderstood that the corresponding bromoketones, iodoketones andfluoroketones may be used.

Preferred alpha-chloroketones are chloroacetone, 1,3- dichloroacetoneand hexachloroacetone. Other chloroketones include 1-chlorobutanone-2,1,3-dichlorobutanone-2, 1,4-dichlorobutanone-2, 1-chloropentanone-2, 1,3-dichloropentanone-2, 1,4-dichloropentanone-2, 1,5-dichloropentanone-2,l-chlorohexanone-Z, 1,3-dichlorohexanone-2, 1,4-dichlorohexanone-2,-l,5-dichlorohexanone- 2, 1,6-dichlorohexanone-2, etc. The abovechloroketones are preferred when the novel composition of matter is usedas an additive to hydrocarbon oils.

For economic reasons, sodium or potassium is preferred as the alkalimetal component, although it is understood that lithium, calcium,magnesium, zinc, cadmium, barium, nickel, copper, etc., may be used. Thereaction is readily effected by refluxing the alkali metal salt of thedithiophosphate and the haloketone in the presence of theoxygen-containing polar solvent.

When the haloketone is reacted with sodium or potassiumdit-hiophosphoric acid, R in the first formula above set forth ishydrogen and the resultant compounds include dithiophosphatyl acetone[which also may be named S- (propyl-2-one)-dithiophosphate],dithiophosphatyl butanone-2, dithiophosphatyl pentanone-2,dithiophosphatyl hexanone-Z, etc. In a preferred embodiment thedithiophosphatyl component preferably contains 1 or 2 alkyl groups, eachcontaining from about 1 to about 20 carbon atoms. Illustrative compoundsformed by the reaction of chloroketones with such dialkyldithiophosphates include 0,0-di-methyl-dithiophosphatyl acetone whichalso may be named 0,0-dimethyl-S-propyl-2-one-dithiophosphate,0,0-diethyldithiophosphatyl acetone, O,O-dimethyl-dithiophosphatylbutanone-Z,0,0-diethyl-dithiophosphatyl-butanone 2,l0,0-dimethyl-dithiophosphatylpentanone-2,-0,0-diethyl-dithiophosphatyl-pcntanone 2,

3 0,0-dimethyl-dithiophosphatyl-hexanone-Z,0,0-diethyldithiophosphatyl-hexanone-2, etc.

When used as an additive in lubricating oil, higher alkyl derivativesare preferred such as Generally the alkyl groups are the same as in thecompounds specifically set forth above, although it is understood thatdifferent alkyl groups may be used as illustrated, for example, incompounds as O-methyl-O-ethyl-dithiophosphatyl acetone,O-ethyl-O-propyl-dithiophosphatyl acetone,O-propyl-O-butyl-dithiophosphaty'l acetone,O-propyl-O-amyl-dithiophosphatyl acetone,O-isopropyl-O-decyl-dithiophosphatyl acetone,O-isopropyl-O-tridecyl-dithiophosphatyl acetone,O-isopropyl-O-pentadecyl-dithiophosphatyl acetone,O-sec-butyl-O-octyl-dithiophosphatyl acetone,O-sec-butyl-O-decyl-dithiophosphatyl acetone,O-sec-butyl-O-tridecyl-dithiophosphatyl acetone,O-sec-amyl-O-octyl-dithiophosphatyl acetone,O-sec-amyl-O-decyl-dithiophosphatyl acetone,O-sec-amyl-O-tridecyl-dithiophosphatyl acetone, etc.

The above specific compounds are examples of products obtained when thedithiophosphate is created in equal molar proportions with amonochloroketone. When the dithiophosphate is reacted in a proportion of2 moles of dithiophosphate to 1 mole of 1,3-dichloroacetone, R" in thefirst formula above set forth is a dithiophosphatyl group. Illustrativecompounds in this embodiment include 1,3-bis-0,0-dimethyl-dithiophosphatyl) acetone,1,3-bis-(0,0-diethyl-dithiophosphatyl) acetone,l,3-bis-(0,0-dipropyl-dithiophosphatyl) acetone, 1,3-bis-(0,0-dibutyl-dithiophosphatyl) acetone,1,3-bis-(0,0-dipentyl-dithiophosphatyl) acetone,1,3-bis-(0,0-dihexyl-dithiophosphatyl) acetone,1,3-bis-(0,0-diheptyl-dithiophosphatyl) acetone,1,3-bis-(0,0-dioctyl-dithiophosphatyl) acetone,1,3-bis-(0,0-dinonyl-dithiophosphatyl) acetone,l,3-bis-(0,0-didecyl-dithiophosphatyl) acetone,l,3-bis-(0,0-diundecyl-dithiophosphatyl) acetone,l,3-bis-(0,0-didodecyl-dithiophosphatyl) acetone,1,3-bis-(0,0-ditridecyl-dithiophosphatyl) acetone, etc.,

and the corresponding bis-(dialkyldithiophosphatyl) butanone-2,pentanone-2, hexanone-2, etc.

The specific compounds hereinbefore set forth comprise those in whichthe dithiophosphate contains two alkyl groups. It is understood thatcorresponding dithiophosphatyl compounds containing only one alkyl groupattached to the phosphorus may be employed, in which embodiment thealkyl group is selected from those hereinbefore specifically set forth.Mixtures of the monoand di-alkyl phosphates are available commerciallyand conveniently are used in accordance with the present invention.

The alpha-substituted dithiophosphatyl ketones are prepared in anysuitable manner and are readily prepared by the reaction of an alkalimetal dithiophosphate with the haloketone. As hereinbefore set forth,when R" in the above formulas is hydrogen or an alkyl group, thedithiophosphate and haloketone are reacted in equal molar proportions.When R" in the above formulas is a dithiophosphatyl group, 2 moleproportions of the dithiophosphate are reacted per 1 mole proportion ofthe haloketone. The reaction is readily effected by refluxing thereactants for a time suificient to accomplish the desired reaction. Thismay range from 0.5 to 48 hours or more and generally will be for a timeof from about 3 to about 20 hours. The refluxing temperature generallywill be within the range of from about 30 to about 150 C. and preferablyabout 50 to about C. The pressure may range from atmospheric to 1000p.s.i.g. or more.

As hereinbefore set forth, it is essential that the reaction is effectedin the presence of a polar solvent. Any suitable oxygen-containing polarsolvent is employed including alcohols, particularly methanol, ethanol,propanol, butanol, etc., ketones including .acetones, methyl ethylketone, diethyl ketone, dipropyl ketone, etc., and glycols,glycolethers, alkylamides, 'dimethyl-formamide, dimethyLacetamide,nitromethane, dimethyl or diethyl sulfoxide, dimethyl ether, diethylether, etc., water or aqueous solutions of the solvents hereinbefore setforth. When desired, either or both of the reactants may be prepared asa solution in the solvent for ease of handling or in forming a morefluid reaction mixture, or the solvent may be added to the reactionmixture. The solvent permits effecting the reaction at lower temperatureand thereby favors the formation of monomers. Polymers are formed at thehigher temperatures. The polymers or polycondensates are not harmful inlubricating oils.

In one method of operation the haloketone and alkali metaldialkyldithiophosphate are formed .as separate solutions in an alcoholicsolvent. The solutions then are mixed, and the mixture is heated andmaintained at refluxing conditions for the desired time. Following thecompletion of the reaction, the desired product is recovered in anysuitable manner. In one method the product is dissolved in an aromaticsolvent, washed with Water and/ or sodium bicarbonate or similarsolution, dried over anhydrous sodium sulfate, anhydrous potassiumcarbonate or the like, and then filtered and heated to remove thearomatic solvent, the latter generally being effected under vacuum.

As hereinbefore set forth, another embodiment of the invention comprisesthe ketal and thioketal derivatives of the alpha-substituteddithiophosphatyl ketone as illustrated by the second formulahereinbefore set forth. These derivatives may be prepared in anysuitable manner and preferably by reacting the desired alcohol ormercaptan with the alpha-substituted dithiophosphatyl ketone in thepresence of an acid catalyst. Any suitable acid catalyst may be used,hydrogen chloride being particularly preferred. In one embodiment thealcohol or mercaptan is used in a proportion of 2 moles thereof to 1mole of the dithiophosphatyl ketone and in another embodiment thealcohol or mercaptan is used in equal mole proportions to thedithiophosphatyl ketone. The reaction readily occurs at ambienttemperature by commingling the reactants, preferably with stirring, inorder to obtain intimate mixing. Usually a slight excess of the alcoholor mercaptan is employed. Followin completion of the reaction, theproduct is dried in any suitable manner, including the use of anhydroussodium sulfate, anhydrous potassium carbonate, etc., and then filteredand distilled, preferably under vacuum, to remove lighter materials.

Any suitable alcohol is used, including methyl alcohol, ethyl alcohol,propyl alcohol, butyl alcohol, pentyl alcohol,

7 pour point depressant, viscosity index improver, detergent, etc.

The lubricating oil may be straight mineral lubricating oil derived fromparaffinic, naphthenic, asphaltic or mixed base petroleum crudes orblends thereof and is generally highly refined. In another embodimentthe lubricating oil is a synthetic lubricating oil and may be one or amixture of various types including aliphatic esters, polyalkyleneoxides, silicones, esters of phosphoric and silicic acids, highlyfluorine-substituted hydrocarbons, etc. Of the aliphatic esters,di-(Z-ethylhexyl) sebacate is being used on a comparatively largecommercial scale. Other aliphatic esters include dialkyl azelates,dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkylglutarates, etc. Specific examples of these esters include dihexylazelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glultarate,di-3,5 ,5-trimethylpentyl .glutarate, di-(2-e thylhexyl) pimelate,di-(2-ethylhexyl) adipate, triamyl tricarbal'lylate, penetaerythritoltetracaproate, dipropylene glycol dipelargonate,1,5-pentanediol-di-(Z-ethyihexanonate), etc. The polyalkylene oxides andderivatives include polyisopropylene oxide, polyisopropylene oxidediether, polyisopropylene oxide diester, etc. The silicones includemethyl silicone, methylphenyl silicone, etc., and the silicates include,for example, tetraisooctyl silicate, etc. Synthetic lubricants proposedfor use in high temperature service as, for example, jet fuellubrication, are pentaerythritol esters and trimethylol propane esters.

The novel composition of the present invention also is useful as anadditive to lubricating greases. These may be either of synthetic orpetroleum origin. The synthetic greases generally are referred to aslithium base grease, sodium base grease, calcium base grease, bariumbase grease, strontium base grease, aluminum base grease, mixed basegreases including barium-calcium base grease, aluminum-calcium basegrease, lithium-strontium base grease, etc. 'These greases are solid orsemi-solid gels and, in general, are prepared by the addition to mineralor synthetic lubricating oils of hydrocarbon-soluble metal soaps orsalts of higher fatty acids as, for example, lithium stearate, calciumstearate,- aluminum napthenate, etc. The grease may contain thickeningagents such as silica, carbon black, .polyacrylates, talc, etc. Anothertype of grease is prepared from oxidized petroleum wax, to which thesaponifiable base is combined with the proper amount of the desiredsaponifying agent, and the resultant mixture processed to produce agrease. Other types of greases in which the features of the presentinvention are usable include petroleum grease, w-hale grease, woolgrease, etc., and those made from inedible fats, tallow, butchers waste,etc.

The novel composition also is useful in the stabilization of polyolefinsand particularly polyethylene. The polyolefins preferably are of highmolecular weight, usually having a molecular weight aboue 1000 andextending into the hundreds of thousand range. Generally these aresynthetically prepared. A typical example is the widely usedpolyethylene plastics. Other polyolefins include polypropenes,polybutenes, and polymers of higher molecular weight olefins. These maybe of the high density, medium density or low density type. Polyethyleneis utilized, for example, as thermoplastic molding or coating agent.Because of its high dielectric strength and its resistance to water,polyethylene is particularly advantageous for use as insulators ordielectrics in condensers and other similar electronic equipment.However, polyethylene is subject to attack by atmospheric oxygen,particularly at elevated temperatures, either in use or duringmanufacture, and this impairs the desirable properties thereofincluding, for example, a reduction in t well as jet fuel, diesel oil,mineral oil, fuel'oil, residual oil, drying oil, Waxes, resins, rubber,etc. These substances are adversely affected by oxygen, with theresultant formation of one or more of undesirable gum, sediment,discoloration, cracking, corrosion, and/ or other deleterious reactions.

When used as an additive to organic substrates, the novel compounds ofthe present invention may be utilized in a concentration of from about0.001% to about 25% by weight of the organic substrate, although in somecases higher or lower concentrations may be employed. The exactconcentration to be used will depend upon the particular substrate to betreated. In most cases concentrations from about 0.01% to about 5% byweight generally will be employed.

It is understood that the composition of the present invention may beused along with other additives incorporated in the organic substrate.For example, one or more of an additional additive including metaldeactivator, dye, viscosity index improver, pour point depressant,anti-foaming additive, lubricity and extreme pressure additive,anti-scuffing additive, detergent, corrosion inhibitor, etc., may beincorporated in the substrate. When desired, the composition of thepresent invention may be prepared as a mixture with one or more of theseother additives and marketed and/or incorporated in the substrate inthis manner.

The composition of the present invention may be incorporated in theorganic substrate in any suit-able manner and at any suitable stage ofpreparation. When incorporated in a liquid substrate, the composition ofmatter is added thereto and intimately mixed by conventional means. Whenadded to a solid or semi-solid substrate, the composition of the presentinvention preferably is added during the manufacture thereof in order toobtain intimate mixing. For example in the manufacture of grease, thecomposition of the present invention may be added to one or more of thecomponents of the grease prior to compositing and processing thereof, orit may be added to the mix at any time, preferably before finalprocessing in order to obtain intimate mixing and dissolving thereof inthe grease. In other cases, a solid substrate may be dipped, soaked orimmersed in the additive, or the latter may be sprayed, brushed orotherwise applied to the solid substrate.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

EXAMPLE I Diisopropyl-dithiophosphatyl acetone (also named 0,0-diisopropyl S propyl 2 one dithiophosphate or 0,0 diisopropyldithiophosphatyl propane 2 one) was prepared as follows: 126 g. (0.5mole) of potassium diisopropyl dithiophosate were dissolved in 200 g. ofmethanol and the mixture was refluxed. 47 g. (0.5 mole) ofchloro-2-propanone were added dropwise to the refiuxing mixture. Thereaction mixture was refluxed for 6.5 hours, following which benzenesolvent was added and the mixture then was filtered to remove potassiumchloride and was washed with hot acetone-methanol. The

product then was Washed with water, dried over anhydrous sodium sulfate,filtered and heated on -a steam bath under vacuum to remove benzene andany lighter dissolved materials. g. of product were recovered, whichcorresponds to the theoretical yield of 134 g. The product isdiisopropyl dithiophosphatyl acetone having a boiling point of IDS-106C. at 0.3-0.35 mm.

Analysis:

Phosphor-us- Percent Found 11.0 Theory 11.48

Sulfur Found 23.3 Theory 23.7

hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decylalcohol, undecyl alcohol, dodecyl alcohol, etc. Similarly, any suitablemercaptan is used including methyl mercaptan, ethyl mercaptan, propylmercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, etc.,benzylmercaptan, thiophenol or thiophenol derivatives aschlorothiophenol, para-nitrothiophenol, ortho-nitrothiophenol,2-chloroethylmercaptan, Z-alkoxymercaptan and, in general, mercaptanscontaining such substituents, as Cl, OH, RO, N0 etc.

Illustrative examples of the thioketal derivatives includedialkyl-dithiophosphatyl-Z,2-methylrnercaptropropane,dialkyl-dithiophosphaty1-2,2-ethylmercaptopropane,dialkyl-dithiophosphatyl-2,2-propylmercaptopropane,dialkyl-dithiophosphaty-l-2,Z-butylmercaptopropane,dialkyl-dithiophosphatyl-2,2-pentylmercaptopropane,dialkyl-dithiophosphaty1-2,2=hexylmercaptopmopane, etc.,dialkyl-dithiophosphatyl-2,Z-methylmercaptobutane,dialkyl-dithiophosphatyl-2,Z-ethylmercaptobutane,dialkyl-dithiophosphatyl-2,2-propylmercaptobutane,dialkyl-dithiophosphatyl-2,2-butylmercaptobutane,dialkyl-dith'iophosphatyl2,2-pentylmercaptobutane,dialkyl-dithiophosphaty1-2,Z-hexylmercaptobutane, etc.,dialkyl-dithiophosphatyl-2,Z-methylmercaptopentane,dialkyl-dithiophosphatyl-2,Z-ethylmercaptopentane,dialkyl-dithiophosphatyl-2,2-propylmercaptopentane,dialkyl-dithiophosphatyl-2,2-butylmercaptopentane,dialkyl-dithiophosphatyl-Z,2-pentylmercaptopentane,dialkyl-dithiophosphatyl-2,Z-hexylmercaptopentane, etc.,dialkyl-dithiophosphatyl-2,Z-methylmercaptohexane,dialkyl-dithiophosphatyl-Z,Z-ethylmercaptohexane,dialkyl-dithiophosphatyl-2,Z-propylmercaptohexane,dialkyl-dithiophosphatyl-Z,2-butylmercaptohexane,dialkyl-dithiophosphatyl-2,Z-pentylmercaptohexane,dialkyl-dithiophosphatyl-2,2-hexylmercaptohexane, etc.,dialkyl-dithiophosphatyll -chloro-2,Z-dimethylmercaptopropane,dialkyl-dithiophosphatyl-Z,2-dimethylmercapto-3- chloropropane,dialkyl-dithiophosphatyl-l,1-dichloro-2,2-dimethylmercaptopropane,dialkyl-dithiophosphatyl-1,l,3-trichloro-2,2-dimethylmercaptopropane,dialkyl-dithiophosphatyl-l,1,3,3-tetrach1oro-dimethylmercaptopropane,dialkyl-dithiophosphatyl- 1 l ,3 ,3 ,3-pentachlorodialkylmercaptopropane, etc., and similarly substitutedcompounds in which the methylmercapto substituent is replaced byethylrnercapto, propylmercapto, butylmercapto, pentylmercapto, orhexylmercapto, as well as similarly substituted butanes, pentanes,hexanes, etc. Other illustrative examples include 1, 3-bis-(dialkyl-dithiophosphatyl) -2,2-

dimercaptopropane, 1,3-bis-(dialkyl-dithiophosphatyl)-2,2-

dimercaptobutane, 1,4-bisdialkyl-dithiophosphatyl -2,2-

dimercaptobutane,

1 3-bis- (dialkyl-dithiophosphatyl -2,2-

dimercaptopentane, 1,4-bis- (dialkyl-dithiophosphatyl -2,2-

dimercaptopentane,

1,5 -bisdialkyl-dithiophosphatyl) -2,2-

dimercaptopentane, 1,3-bis-(dialkyl-dithiophosphatyl)-2,2-

dimercaptohexane, 1,4-bisdialkyl-dithiophosphatyl) -2,2-

dimercaptohexane, 1,S-bis-(dialkyl-dithiophosphatyl)-2,2-

dimercaptohexane, l,6-bis-(clialkyl-dithiophosphatyl)-2,2-

dimercaptohexane, etc., 1,3-bis-(di alky-l dithiophosphatyl)-l-chloro2,2-

mercaptopropane,

1,3-bis- (dialkyl-dithiophosphatyl) l l-dichloro-2,2-

mercaptopropane,

1,3-bis-(dialkyl-dithiophosphatyl) -1, 3-dichloro-2,2-

mercaptopropane,

1,3-bis-(dialkyl-dithiophosphatyl) -1,1,3 -trichl0ro-2,2-mercaptopropane,

1,3 -bis- (dialkyl-dithiophosphatyl) -1, l ,3 ,3-tetrachloro-2,2-mercaptopropane,

1,3 -bis-(dialkyl-dithiophosphatyl)-1,1,3 ,3 -tetrachloro-2,2-dialkylmercaptopropane, etc., and

similarly substituted dithiophosphatyl butanes, pentanes, hexanes, etc.In another embodiment only one mercapto substituent is attached to theNo. 2 carbon atom and these compounds will correspond to thosehereinbefore specifically set forth, except for the single mercaptogroup.

The ketal derivatives will correspond to the thioketal derivativeshereinbefore set forth, except that the mercapto group will be replacedby an alkoxy group as illustrated, for example, in compounds asdialkyl-dithiophosphatyl-2-methoxypropane,

dialkyl-dithiophosphatyl-2-ethoxypropane,

dialkyl-dithiophosphatyl-2-propoxypropane,

dialkyl-dithiophosphatyl-2-butoxypropane, etc.,

dialkyl-dithiophosphatyl-2,2-dimethoxypropane,

dialkyl-dithiophosphatyl-2,2-diethoxypropane,

dialkyl-dithiophosphatyl-2,2-dipropoxypropane,

dialkyl-dithiophosphatyl-2,2-dibutoxypropane, etc.,

dialkyl-dithiophosphatyl-1-chloro-Z-methoxypropane,

dialkyl-dithiophosphatyl-1,1 -dichloro-2- methoxypropane,

dialkyl-dithiophosphatyl-1,3 -dichloro-2- methoxypropane,

dialkyl-dithiophosphatyl-1,1,3 -trichloro-2- methoxypropane,

dialkyl-dithiophosphatyL1,1,3 ,3-tetrachloro-2- methoxypropane,

dialkyl-dithiophosphatyl-1,1,3, 3,3-pentachloro- 2,2-dimethoxypropane,

dialkyl-dithiophosphatyl-1,1, 3 ,3 ,3-pentachloro- 2,2-diethoxypropane,etc.,

1,3-bis- (dialkyl-dithiophosphatyl) -2- methoxypropane,

1,3 -bis- (dialkyl-dithiophosphatyl) -2,2-

dimetho xyprop ane,

1,3-bis-(dialkyl-dithiophosphatyl)-1-chloro-2- methoxypropane,

1,3-bisdialkyl-dithiophosphatyl l-chloro-2,2-

dimethoxypropane,

1,3 -bis-(dialkyl-dithiophosphatyl)l,1-dichl0ro-2,2-

dimethoxypropane,

1, 3-bisdialkyl-dithiophosphatyl) l ,3 -dichloro-2,2-

dimethoxypropane,

1,3-bisdialkyl-dithiophosphatyl) l l ,3-trichloro-2,2-

dimethoxypropane,

l,3-bis-(dialkyl-dithiophosphatyl)-l,1,3 ,3-tetrachloro-2,2-

dimethoxypropane, etc.,

as Well as correspondingly substituted dithiophosphatyl butanes,pentanes, hexanes, etc. It is understood that these are illustrativeexamples and that the alkyl groups will be selected from thosehereinbefore specifically set forth and that other modifications withinthis class of compounds are included within the broad scope of thepresent invention.

From the hereinbefore description, it will be seen that a large numberof novel compounds are comprised Within the present invention.

The novel composition of matter of the present invention is particularlyuseful as an additive to hydrocarbon oil and still more particularly tolubricating oil. In the latter oil, the compound serves a number ofimportant functions such as oxidation inhibitor (peroxide decomposcr),bearing corrosion inhibitor, ring anti-plugging additive, extremepressure additive, anti-friction additive,

9 EXAMPLE II 1,3 bis (0,0 diisopropyl dithiophosphatyl)- propane-2-onewas prepared as follows: 25.4 g. (0.2 mole) of 1,3 dichlor-o 2 propanonewere added dropwise to a refluxing solution of 100.8 g. (0.4 mole) ofpotassium diisopropyl dithiophosph-ate in 200 g. of Formula 30 alcohol(primarily methanol). Following completion of the reaction, the productwas dissolved in benzene, washed with water, washed with a solution ofsodium bicarbonate, water washed again, dried over anhydrous sodiumsulfate, filtered and heated on a steam bath under vacuum to removebenzene and lighter materials. The final product was recovered in ayield of 84 g., which corresponds to the theoretical yield of 96.6 g.The product is 1,3-bis-(0,0-diisopropyl-dithiophosphatyl)-propane-2-one.

Analysis:

EXAMPLE HI 1,3 bis (0,0 ditridecyl dithiophosphatyl) propane-2-one wasprepared as follows: 165 g. (0.3 mole) of 0,0 ditridecyl dithiophosphatewere reacted with 19.5 g. of potassium hydroxide in 200 g. of Formula 30alcohol to prepare the potassium salt. While refluxing this solution, 30g. of chloroacetone were added dropwise and the refluxing continued fora total of 5 hours. The precipitated potassium chloride was dissolved inwater and the product was extracted with benzene, washed twice withwater, dried over anhydrous sodium sulfate, filtered, and the benzeneand lighter materials removed by heating under vacuum on a steam bath.1,3-bis-(0,0-ditridecyl dithiophosphatyl) propane 2 one was recovered asa dark amber oily liquid in a yield of 170 g.

EXAMPLE IV The thioketal derivative of 0,0 diisopropyl dithiophosphatylpropanone 2 one, prepared as described in Example I, was prepared byreacting 67.5 g. mole) of this dithiophosphatyl propanone-2 with 34 g.(/2 mole) plus excess of ethyl mercaptan in the presence of anhydroushydrogen chloride. The reactants were commingled at room temperature andan exothermic reaction resulted. An additional 34 g. of ethyl mercaptanwere added to replace the loss due to evaporation. Following completionof the reaction, the product was dried over anhydrous sodium sulfate,filtered and distilled under vacuum on a steam bath. The yield of thedesired product was 79 g.

Analysis:

Phosphorus- Percent Found 8.12 Theory 8.24

Found 32.34 Theory 34.05

EXAMPLE V The ketal derivatives of 1,3-bis-(0,0-diisopropyldithiov 10EXAMPLE VI 1,3 bis (dithiophosphatyl) 1,3 dichloro propanone-2 isprepared by reacting 2 mole proportions of the sodium salt ofdithiophosphoric acid with 1 mole proportion of1,1,3,3-tetrachloroacetone under refluxing conditions in the presence ofisopropanol solvent. Following completion of the reaction, the reactionmixture is dissolved in benzene, filtered, washed, dried and distilledunder vacuum.

EXAMPLE VII 1,3 bis (0,0 dimethyl dithiophosphatyl) 1,1,3,3-tetrachloropropanone-Z is prepared by reacting 2 mole proportions of thesodium salt of 0,0-dimethyl-dithiophosphate with 1 mole proportion ofhexachloroacetone runder refluxing conditions in the presence ofisopropanol solvents. After the rea-ction is completed, the reactionmixture is dissolved in benzene, filtered, washed, dried and distilledunder vacuum.

EXAMPLE VHI As herein'before set forth, the compounds of the presentinvention are particularly advantageous for use as additives tolubricating oil. The present example illustrates the effectiveness ofthe compounds of Examples I and IV as additives in a typicalparaflinic-solvent extracted lubricating oil evaluated in a Lausonengine. For this series of tests the runs were continued for 115 hours,except for the control run without additive which was discontinued after24 hours because of seizure occurring, using a jacket temperature of 210F. and an oil temperature of 280 F. Pertinent results of these runs arereported in the following table.

Table 1 Run Number 1 2 3 0.57 by 0.57 by Additive None weight of weightof Example I ExampleIV Product Product Bearing wt. loss, g-ms 2. 90210.0050 0. 0175 Oil consumption, ml./hr 6. 03 4. 64 6.88 Used Oil:

Neutralization No 10. 78 0.37 0. 62 Saponification N0., Mg.KOH/gm 25. 94. 23 Pentane insolubles, percent 5.16 0. 47 0. 19 Viscosity, SSU at F742 296 295 From the data in theabove table, it will be noted that thenovel compounds of the present invention were very effective in reducingcorrosion, as evidenced by the very low bearing weight losses in runs 2and 3 as compared to run number 1 which was made in the absence of theadditive. Also, the compounds were effective in preventing undesiredchanges in the lubricating oil, as evidenced by the neutralizationnumber, saponificat-ion number, percent pentane insolubles andviscosity.

EXAMPLE IX An evaluation similar to that described in Example VIII wasmade for the compound of Example II. This run was made in the samemanner as described in Example VII and the pertinent results are shownin the following where O is oxygen, S is sulfur, P is phosphorus, C iscarbon, R and R are selected from the group consisting of hydrogen andalkyl radicals, R is selected from the group consisting of hydrogen,alkyl, halogen and 0,0-dialkyldithiophosphatyl radicals, X is selectedfrom the group consisting of hydrogen and halogen radicals, Y isselected from the group consisting of oxygen and sulfur, and R isselected from the group consisting of hydrogen and alkyl radicals, saidalkyls each containing from 1 to about 20 canbon atoms.

2. Lubricating oil containing a stabilizing concentration of aninhibitor comprising dialkyl-dithiophosphatyl acetone in which eachalkyl contains from 1 to 20 carbon atoms.

3. Lubricating oil containing a stabilizing concentration ofdiisopropyl-dithiophosphatyl acetone.

4. Lubricating oil containing a stabilizing concentration ofditridecyl-dithiophosphatyl acetone.

5. Lubricating oil containing a stabilizing concentration of 1,3bis-(dialkyl-dithiop'hosphatyl)-acetone.

6. Lubricating oil containing a stabilizing concentration of1,3-bis-(diisopropyl-dithiophosphatyl)- acetone.

References Cited by the Examiner UNITED STATES PATENTS 2,632,020 3/1953Hoegberg 252-46.6 2,794,041 5/1957 Norman et .al. 252 46.6 2,948,6828/1960 Crosby (it al. 252-46.6 3,105,003 9/1963 Walsh et a1. 260-461DANIEL E. WYMAN, Prim ry Examiner.

L. G. XIARHOS, Assistant Examiner.

1. ORGANIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF HYDROCARBONS,LUBRICATING OILS AND GREASE CONTAINING A STABILIZING CONCENTRATION OF ANINHIBITOR HAVING A STRUCTURAL FORMULA SELECTED FROM THE GROUP CONSISTINGOF: